Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
':
Title . Process and reactor for exothermic heterogeneous
synthesis with several catalytic beds and heat
exchange.
D E S C R I P T I O N
This invention concerns a process for exothermic
heterogeneous synthesis in which the synthesis gas flows over
a series of catalytic beds superimposed bait separate one from
the other contained within the same reaction space, all the
reacted gas collects in the central zone of the last lower
catalytic bed and from here it flows upwards to the top of
said space inside which its heat is exchanged and steam is
produced.
The invention also concerns reactors to put this process into
effect, consisting of a pressure-resistant external shell, of
baskets of catalytic beds all inside the same shell, of a
cartridge and of a heat exchanger.
In a recent patent application it was pointed out that in
ammonia production a remarkable amount of heat is developed
in the synthesis reaction N2+3H2, which is generally
recovered for the final purpose of producing steam recycled
to reduce energy consumption.
4
l
The most advanced technology tends towards maximum recovery
of said synthesis heat at the highest possible thermic level;
synthesis units and their main component, the reactor, are
therefore designed to this end.
The reactors used in new plants have several catalytic beds
with intermediate quenching of the gas by means of indirect
exchange through heat exchangers; moreover part of the
reaction heat is removed with an external cooling fluid such
as for example water feeding a boiler or by means of
generating steam before the last reaction stage, and this for
the purpose of being able to operate at the highest possible
temperature (heat recovery at maximum thermic level) without
any limitations of the greatest possible efficiency
obtainable.
Maximum 'temperature and maximum yield are in fact contrasting
needs as amply shown by the relevant diagrams which indicate
in abscissa the concentration of ammonia and in ordinate the
temperature of the gas.
Major synthesis reactor designers in general have favoured
reactors with several catalytic beds in at least two distinct
parts in series, in order to satisfy the above-mentioned need
for the optimal exchange of reaction heat (at the highest
thermic level) without limiting the maximum yield obtainable
(Fertilizer Focus October '1987).
CA 02011886 2000-08-09
Where two distinct parts of equipment are adopted, the first
of the two reaction devices generally contains two catalytic
beds with indirect intermediate quenching with an internal
heat exchanger, while the second one generally contains a
single catalytic bed.
Heat exchange between the two parts of the installation is
carried out by introducing a boiler to produce steam. This
is the case with the Topsoe Series 250 (Series 200 + Series
50) reactor and with the Uhde reactor, both of them with
radial flow of the gas in the catalytic beds (Fertilizer
Focus October 1987, pages 36 and 39).
There are also reactors in three distinct parts, each part
containing a catalytic bed with axial gas flow as found in
the C.F. Braun design (Nitrogen Conference, Amsterdam 1986).
In this case a steam-producing boiler is inserted between the
second and the third part of the installation (Nitrogen
Conference, Amsterdam 1986, Mr. K.C. Wilson, Mr. B.J. Grotz
and Mr. J. Richez of CdF Chimie).
According to a recent patent by C.F. Braun (US Patent
4554135 issued 19 Nov. 1985), the gas/gas exchanger between
catalytic beds, usually conveniently situated inside the
reactors with at least two beds inside a single installation,
is situated outside the reaction apparatus directly connected
to the bottom of the shell containing a single catalytic bed.
6
To minimize the problems of pipes at a high temperature, the
tube connecting the above horizontal exchanger with the shell
containing the catalytic bed is quenched with the fresh gas
fed to the reactor.
After having pre-heated the fresh feed gas, the gas leaving
the catalytic bed leaves from the exchanger and feeds the
device containing the second catalytic bed (C. F. Braun
reactor with several reaction devices as shown in Fig. 5 of
the Wilson, Grotz, Richez report of the above-mentioned
reference and at page 48 of Fertilizer Focus, October 1987).
The problem solved in the C.F. Braun patent mentioned above,
i.e. avoiding contact between high temperature gas and the
tubes connecting shell and exchanger, does not affect
reactors with several catalytic beds within a single piece of
apparatus since, as described above, the gas/gas exchanger is
inserted directly inside the reactor itself.
Even according to C.F. Braun the problem of optimal heat
exchange is solved in a complex way by introducing a boiler
connected by means o:E complex piping to the reactor itself
(see Fig. 5 of the C.F. Braun presentation, Nitrogen '86 and
Fertilizer Focus October 1987, page 48).
All the above plans, although resolving the thermodynamic
problem, are very complex, hence very expensive.
7
CA 02011886 2000-08-09
Ammonia synthesis reactors operate in fact at high pressure,
generally not below 80 bar, and more often between 130 and
250 bar, and at a high temperature (400:500°C). The
connecting tubes for the various pieces of equipment
necessary according to the drawings described above (as shown
schematically in the above-mentioned references), operate
under critical conditions (high temperature of the gas
between the various reaction beds) and must therefore be made
of special material and with long runs to minimize the
mechanical stress resulting from thermic dilation. the
situation is particularly complex in reactors according to
C.F. Braun, in spite of the measures taken according to the
C.F. Braun U.S. Patent No. 4554135 issued 19 November, 1985.
In the above-mentioned recent patent application the
Applicants have suggested a process and a reactor with
several catalytic beds which do not suffer from the drawbacks
described above, can be produced in a single piece, and
permit the easy removal of reaction heat between catalytic
beds, and more particularly before the last catalytic bed, so
as to achieve maximum recovery of reaction heat at the
highest thermic level, such heat being exchanged, for
example, to pre-heat boiler water or to produce steam
directly.
The hot gas reacted in the last catalytic bed but one is
transferred, through a duct generally situated along the axis
8
~~~~~8~
of the vertical reactor, directly to the heat exchange system
pre-heater or boiler), returning then directly to the
reactor through a duct, either internal or external to the
above-mentioned transfer duct, creating an airspace for the
gas to run through, returning to the reactor, said gas
feeding then directly the last catalytic bed with an axial-
radial or radial flow either centrifugal or centripetal.
Said gas, after reacting in the last catalytic bed, is
transferred once again to the central or external part of the
reactor, and leaves then from the bottom of the reactor.
This system works very well with reactors with a cylindrical
shell with a substantially constant diameter, but would meet
some difficulties with reactors having a graduated diameter
shell.
Continuing in their research and experiments, the Applicants
have now found that, especially when using and modernizing
bottleneck-type reactors, it is advantageous to introduce the
pre-heater or boiler inside said neck, collect the reacted
gas in the central zone of the last bed, remove it and send
it upwards axially and centrally to the top or neck where its
heat is recovered.
To facilitate comprehension of the system, subject of this
invention, it is now described with reference to the
illustration representing a cross-section by way of example
9
CA 02011886 2000-08-09
~~11~$~
of the converter according to a preferred embodiment of the
invention.
The reactor consisting of shell (1) and of cartridge (2)
forming the catalytic beds (in this case 3, namely 6, 7 and
13) is fed by the fresh gas (3) entering from the bottom of
the reactor and running through from bottom to top of the
airspace (4) between the shell (1) internal wall and the
cartridge (2) external wall, for the purpose of reducing to a
minimum the temperature of the shell.
As amply described in other patent applications by the
Applicants, the synthesis gas leaving from the top of the
airspace (4) runs with an axial flow through the smaller
upper portion of the first bed (6) (defined by height "h",
unperforated, of the internal wall Pi1), and with radial flow
the greater portion defined by perforated height "H".
The gas reacted on the first bed (6) collects in the annular
central zone X1 and from here goes to penetrate the second
bed (7) through which it flows axially and radially.
The gas reacted on the second bed collects in internal
annular zone X2. From here, after exchanging heat with fresh
gas (Q2) in exchanger (5) it goes on to the third and last
bed through which it flows both axially and radially
collecting in zone X3.
More particularly, the embodiment shown in the illustration
is substantially of the type described and claimed in Swiss
Patent Application No. 04551/88-8 of 9.12.1988. It
comprises, besides the three catalytic beds (6, 7 and 13),
quenching Q1 at the top of the first bed and a heat exchanger
(5) which is situated centrally through the first and second
bed (6 and 7) and is fed with fresh gas Q2. As described in
said patent application the bottoms of the two catalytic
baskets (6 and 7) have an inverted curve as compared to the
curve of the bottom of the third bed (13).
According to the main feature of this invention, the gas
reacted on the third bed 13 collects in central space X3 and
from here is sent through tube T to the upper end (COL) of
shell (1), where the heat exchanger (RC) for said reacted gas
is situated. RC can be a pre-heater far water (introduced
far example from A) or a boiler generating steam (at a high
level) leaving from (V).
The upper end (COL) of (RC) is solid with the shell (1) of
which it is an extension while the cartridge (4) is closed at
4' on the lower part of RC.
The structure of a reactor with boiler incorporated in the
upper part of the reactor has proved in itself (not
unsurprisingly) the ideal solution to achieve maximum heat
recovery in new high-yield reactors.
11
The same solution has proved a winner when modernizing in
situ the more reliable and generally used old reactors still
in operation at the present time, i.e. Kellogg bottleneck
type reactors. It has been found that with a few marginal
modifications old-type reactors with high energy consumption
can be transformed in situ into high-yield and minimum energy
consumption reactors with axial-radial flow such as for
example the reactors according to US patents 4,372,920 and
4,405,562 by the Applicants carrying out their modernization
in situ according to the system found in US Patent 4,755,362,
again by the Applicants.
In carrying out the transformation according to this
invention, the typical outline of the Kellogg bottleneck
reactor is maintained; inside 'the reactor three catalytic
beds (6, 7 and 13) are introduced with quenching (Q1) and an
exchanger (5) (alternatively, two exchangers), a boiler (for
example a bayonet or hairpins type) is installed in the neck
(COL), the width dirnensions of the old and bulky Kellogg
reactor (for example ID = 2946 mm) are maintained, and
reversed bottoms are given to the first two beds to achieve
maximum pressure and efficiency of the catalyst with a small
granulometry.
By way of example, it has been found that with a reactor
according to this inventian, with a capacity of 1000 MTD, at
a pressure of 140 bar abs, feed gas at 218°C and a volume of
12
catalyst (with granulometry between 1.5 and 3 mm) of 70 m3,
heat recovery in the pre-heater BFW and in the boiler (RC)
can be achieved of. 634'000 Kcal/MT of ammonia (equal to a
production of about 1170 kg/MT of steam at 110 ata, starting
from BF4V at 105°C.
As indicated above, together with the advantages resulting
from heat recovery there is also the further advantage
arising from the possibility of being able to maintain the
configuration and layout of bottleneck reactors, well known
for their simplicity, reliability, efficiency and low costs.
13
